Triamino-triazoles and their production



United States Patent 3,222,375 TRIAMINO-TRIAZOLES AND THEIR PRODUCTIONFritz Wiloth, Klingenberg, and ErwinSommer, Obernburg, Germany,assignors to Vereinigte Glanzstoff- Fabrilren A.G., Wuppertal-Elberfeld,Germany No Drawing. Filed July 11, 1962, Ser. No. 209,234 Claimspriority, application Germany, July 19, 1961,

V 21,021; Mar. 28, 1962, V 22,256 9 Claims. (Cl. 260-308) This inventionis directed to a process for the production of triarnino-triazoles, andmore particularly, the invention is concerned with the production of aclass of l'lOVClq compounds which can be more specifically designated asbis-3,5-(w-amino-alkyl)-4-aminotriazoles. The triamino-triazolecompounds produced according to this invention have a number of uses,particularly as raw materials or intermediates for making dyestuffs,pharmaceuticals and polymers of the type known as linear polyamides andpolyesters. Since all of the compounds pos sess three amino substituentsand a reterocyclic ring, the broad functional utility of these compoundsin a number o-fdifferent fields such as those indicated will be readilyappreciated by one skilled in the art.

It is known that carboxylic acids, carboxylic acid esters,i-minocarboxylic acid esters and nitriles can be reacted with hydrazinein order to form certain dihydrotetrazine compounds. Under certainconditions, the dihydrotetr-azine intermediates can be rearranged intocorresponding monoamino-triazole compounds. In general, most triazolecompounds appear to require a method of production involving more thanone step, i.e., the preparation of an intermediate cyclic compoundfollowed by rearrangement or preparation of an open-chain intermediatefol-lowed by cyclization.

One object, of the present invention is to provide a novel method forthe production of certain tri-amino-triazolesin a single step fromreadily available and relatively inexpensive initial materials.

Another object of the invention is to provide a method of producingtriamino-triazoles which can be carried out in a simple manner and whichleads to a high yield of the desired product in very pure form. Thus, itis an object of the invention to avoid the formation and isolation ofintermediate products and also to avoid by-products which wouldcontaminate the directly obtained triamino-triazole.

It in a further object of the invention to provide novelpolycondensa-tes, such as polyamides and polyesters, wherein thetriarnino-triazoles of this invention have been incorporated asmodifiers to improve the properties of the polycondensate product.

These and other objects and advantages of the invention will become morereadily apparent upon consideration of the following detailedspecification.

In accordance with the invention, it has now been surprisingly foundthat lactams can be reacted with hydrazine at a temperature betweenabout 150 C. and 250 C., preferably from about 180 C. to 230 C., and inthe presence of an inert gas in order to directly producetriamino-triazoles having the formula 3,222,375 Patented Dec. 7, 1965wherein R represents a member selected from the group consisting of C Hand n representing an integer of from 3 to 7, inclusive.

This reaction between the lactam and hydrazine is preferably carried outin a closed vessel, for example in a bomb tube or in an autoclave whichmaybe enamelled or may be constructed of stainless steel with a glasslining, In this closed vessel, a reaction pressure .will be reachedwhich corresponds to the reaction temperature. In other words, it isunnecessary to work at a predetermined pressure, and it is mostconvenient to permit the pressure to introduce the hydrazine into thereaction as hydrazine hydrate (N H .H O), although it will be understoodthat.

hydrazine itself is the essential reactant. Nitrogen orany. other inertgas can be used as a protective medium for the reactants in the closedvessel. After the reaction has been completed, water and any excesshydrazine are.

readily removed, preferably by distillation under reduced pressure, andthe triamino-triazole end product is precipitated with very good yields.The end product can then be purified by vacuum distillation or byextraction andrecrystallization according to conventional purificationprocedures.

The lactams to be used in the reaction with hydrazine according to theinvention can be defined as heterocyclic organic compounds containingthe divalent group NH.CO- in a cyclic ring which otherwise contains onlycarbon and hydrogen atoms. Such rings are generally formed by theelimination of water from a saturated aliphatic amino carboxylic acid.Those lactams are pre ferred which in addition to the -NH.CO-- groupcontain from 3 to 7 carbon atoms in the cyclic structuref The followinglactams are especially useful for the purposes of this invention:pyrrolidone; piperidone; caprolactam; enanthlactam; capryllactam; theC-lower alkyl-substituted lactams, eg. as obtained by the cycliccondensation of gammaor delta-amino carboxylic acids, such as C-'methylor C-ethyl-caprolactam; and-endolactams, such as hexahydro-p-aminobenzoic acid lactam. In general, it is preferred to produce a unitaryproduct by employing a single lactam reactant, but a mixture of productscan be obtained in which R of the above formula will vary de pendingupon the incorporation of ditferent lactams as a mixture of initialreactants.

The production of triamon-triazoles by the method of this invention isfurther illustrated by the following examples, it being understood thatthese examples are merely representative and not intended to beexclusive.

Example 1.Pr0ducti0n of bis-3,5-(w-amin0pr0pyl)-4- aminotriazole: 17 g.of pyrrolidone are heated with 40 g.

of freshly distilled 100% hydrazine hydrate in a bomb tube under anitrogen atmosphere for 6 hours at 210 C. After distilling olf theexcess hydrazine and water on a boiling water bath under reducedpressure, there remains a colorless, viscous oil, which is purified byvacuum distillation at 260-265 C. and 0.01 mm. Hg. The product is acolorless, water-soluble, crystalline mass with a melting point of 68-72C. The yield is 75% of the theoretical amount.

Example 2Pr0duction of bis-3,5-(w-aminpentyl)-4- aminotriazole: 22.6 g.of e-caprolactam are heated with 40 g. of freshly distilled 100%hydraine hydrate in a bomb tube under a nitrogen atmosphere for 6 hoursat 220 C. After distilling off the excess hydrazine and water on aboiling water bath under the reduced pressure of a water jet vacuum,there remains after cooling a colorless, crystalline mass. This mass isextracted for 12 hours with ether in a Soxhlet and is recrystallizedfrom ethyl acetate which is employed in an amount of about lO-12 timesthe amount of the triazole product. The recrystallized product isobtained as colorless needles or flakes which are soluble in water andinsoluble in ether, and which have a melting point of 89-91 C. The yieldis 50% of the theoretical amount.

Example 3.-Pr0a'ucti0n of bis-3,5-(w-amin0pentyl)-4- amin0triaz0le.-1130g. of e-caprolactam are heated with 2000 g. of freshly distilled 100%hydrazine hydrate in a IO-liter autoclave of stainless steel with aglass inset or lining for 6 hours under a nitrogen atmosphere at 210 C.The pressure rises during the process to 50-60 atmospheres. The triazoleproduct is then isolated and purified as described in Example 2. Theyield is 55% of the theoretical amount.

As in the three preceding examples, the remaining lactams recited abovemay be reacted in an identical manner with hydrazine in order to obtainthe corresponding triaminotriazoles. These triamino-triazoles areparticularly useful as modifiers for linear fiber-formingpolycondensates commonly referred to as polyamides and polyesters. TheN-amino group in the triamino-triazoles imparts improved dyeability tothe polycondensate fiber, even when the modifier is present in thecondensed chain only in very small amounts, without substantiallychanging the other desirable properties of the fiber, e.g., high meltingpoints, pinnability and the like. When employed for this purpose, R inthe above formula of the tr-iamino-triazole compound can contain from 2to 11 carbon atoms in a linear or branched alkylene chain, but 3 to 7carbon atoms are still preferred in view of the greater availability ofthe initial reactants and the relative ease of making such compounds.

In order to modify the polyamide or polyester, the polycondensate orlinear polymer is prepared in the usual manner and the triamino-triazoleis added to the monomeric or precondensate reactants or to the moltenpolycondensate. The triamino-triazole additve s thereby incorporatedinto the polymer molecule or is attached at the end of the moleculechain. After spinning and drawing fibers, the modified polyamide orpolyester has an improved affinity for dyestuffs without losing othervaluable properties with respect to use as a textile material.

The above-mentioned triamino-triazole modifiers may be used as freeamines or also as salts of a dicarboxylic acid or an inorganic acid.Since the NH group, which is attached to the nitrogen atom, i.e., theamino group nuclearly-substituted in 4-position, has a relatively lowbasicity, it does not react on mild acylation. Therefore, it is alsopossible to produce precondensates by condensation of thetriamino-triazoles with dicarboxylic acids, their esters or acidchlorides, and to add these precondensates as the modifier to thepolyamide or polyester at a suitable phase of the condensation reactionor n subsequent manufacture or further processing. Polyamides andpolyesters are not previously known which contain in the molecule chainthe structural element H II 1 NH-RO CRNHOOR-O ol \N 1 5 x (in which Rstands for an aliphatic or aromatic hydrocarbon radical, e.g.hexamethylene or para-phenyl, which may be further substituted in knownmanner, and X signifies the degree of polymerizationin mixed polyamidesor polyesters, X=l is also possible). This structural element is thecarrier of the special properties of the polyamides and polyestersaccording to the invention.

Although the triamino-triazole compounds are generally useful with allsynthetic fiber-forming polyamides and polyesters, it will be recognizedthat it is particularly desirable to modify commercial polyamides suchas polycaprolactam and polyhexamethylenediamine-adipate (nylon) orpolyesters such as polyethylene-terephthalate (Dacron). These andsimilar polycondensates, as *well as the monomers from which they areproduced, are adequately described in the literature directed tosynthetic fibers.

In the production of a modified nylon, it is most convenient to add thetriamino-triazole as the salt of adipic acid to the usual monomerichexamethylenediamineadipate, sometimes referred to as the AH-salt.However, the triamino-triazole may also be added when forming theAH-salt or can be added as the adipate prior to or during condensationof the AH-salt.

In the production of a modified polyamide of caprolactam, thetriamino-triazole can likewise be added as the salt of adipic acid, orit can be added as a reaction product with adipic acid dichloride orwith oxalic acid diesters before or during the polycondensation.

Also, when modifying polyesters such as polyethylene terephthalate, itis possible to react the triamino-triazole with the monomeric acidcomponent prior to condensation. For example, the salt of thetriamino-triazole and the acid component of the polyester or anothersuitable dicarboxylic acid, or the reaction product of thetriamino-triazole with acid chlorides or acid esters can be produced andthen added to the reaction charge before or during the polycondensationor even only during further processing.

The additives represented by the triamino-tn'azole compounds arecontained in the modified polycondensates in amounts of about 0.1 to 10molar percent, preferably from 0.5 to 2 molar percent. If precondensatesor salts are used, then the same quantitative data should be observed byreference to monomeric units.

Thus, the term molar percent is employed herein as defined by theformula: T/M where T is the number of mols of the triamino-triazolemonomeric unit and M is the total number of mols of all monomeric units.Each monomeric unit is derived from a single compound such ashexamethylene diamine, adipic acid or caprolactam in the case ofpolyamides and terephthalic acid in the case of polyesters.Precondensates or monomeric salts thus contain at least two monomericunits.

Some salts of the above-mentioned triamino-triazole compounds having thefollowing properties:

Bis-3 ,5 w-aminopropyl) -4-aminotriazole-adipate colorless crystallinepowder from ethanol; melting point of 193194 C. with splitting off ofwater.

Bis-3 ,5 w-aminopropyl -4-aminotriazole-terephthalate colorlesscrystalline powder from ethanol; melting point of 249-252 C. withsplitting off of water.

Bis-3,5-(w-aminopentyl)-4-aminotriazole-adipate: colorless needles fromethanol; melting point of l76177 C. with splitting off of water.

Bis-3,5-(w-aminopentyl)-4-arninotriazole-terephthalate:

colorless crystalline powder from water-ethanol; melting point 269-270C. with splitting off of water.

Bis-3,5-(w-aminopentyl)-4-arninotriazole-oxalate: colorless needles fromethanol; melting point of 165-180 C. with splitting ofi of water.

Bis 3,5-(4-aminocyclohexyl)-4-aminotriazole-adipate: colorless glassymass which can be triturated to a fine powder without defined meltingpoint.

The method of producing the modified polycondensates is explained indetail with the aid of the following examples.

(In the examples, the molecular Weight of the polymers is characterizedby the Staudinger index Z,, of solution viscosity. The Z values aremeasured in 82.5% formic acid at 20 C. in an Ostwald viscosimeter andextrapolated to zero concentration.)

Production of precondensates Example 4.-5.08 g.bis-3,5-(w-amin0pentyl)-4-aminotriazole are dissolved together with 1.6g. NaOH in 200 ml. of water. The solution is treated in a vessel withanother solution of 4.06 g. of isophthalic acid dichloride in 200 ml. ofmethylene chloride, and the mixture is rapidly agitated for 2 minutes at5000 rpm. The polymer precipitating in solid form is drawn 01f, treatedwith water and dried. The Z, value of the product is 2.l6 10' themelting point is about 150l55 C.

Example 5.-In a vessel having a high-speed agitator, a solution of 2.06g. of adipic acid dichloride in 200 ml. of ethylene chloride is treatedwith a solution of 2.86 g. bis-3,5-(w-aminopentyl)-4-aminotriazole and0.82 g. of NaOH in 30 ml. of water, and the mixture is agitated for 2minutes at 5000 r.p.m. The colorless polymer, at first somewhat sticky,is agitated for several hours with water, drawn off and dried in avacuum. The Z,, value of the product is 2.40 the melting point is190-195 C.; the product is partly soluble in boiling water.

Example 6.--A solution of 9.80 g. of oxalic acid diethyl ester in 50 ml.of ethanol is mixed with a solution of 13.29 g.bis-3,5-(w-aminopropyl)-4-aminotriazole. The resulting mixture is wellagitated for about minutes until the temperature of the reaction mixtureagain falls. After several hours the product is drawn off, rewashed anddried. The Z,, value of the product is l.50 l0 the melting point isabout 250-255" C.; the product is soluble in hot water.

Production of modified condensates Example 7.2830 g. e-caprolactam areheated with a solution of the salt ofbis-3,5-(w-aminopentyl)-4-aminotriazole and adipic acid in 280 g. ofwater under exclusion of air in a 10-liter autoclave, at first for 1hour under a steam pressure of its own of 18 atmospheres (gauge) andthen, after gradual release to normal pressure, for a total of 3.5 hoursup to 270 C. The condensate is drawn off as a filament, cut up andextracted by boiling for several hours with Water. Extract content 10%;melting point 2l62l8 C.; Z,, l0 =8.30 (after extraction); soluble in theusual polyamide solvents.

Example 8.22.6 g. e-caprolactam are polymerized with the addition of0.85 g. of the salt of bis-3,5-(4- aminocyclohexyl)-4-amino-triazole andadipic acid in a closed glass tube under nitrogen vacuum for 50 hours at220 C. while shaking. The colorless condensate has an extract content of8.0%. Melting point 2152l7 C.; Z,, 10 =6.60 (after extraction); solublein the usual polyamide solvents.

Example 9.Under the same conditions as described in Example 7, butwithout theaddition of the triaminotriazole compound, a controlcondensate was produced. Extract content 10% melting point 216218 C.;Z,, 10 =7.85 (after extraction).

Example 10.2500 g. of extracted cuttings of poly-ecaprolactam producedaccording to Example 9 were intimately mixed with a solution of 28 g.bis-3,5-(w-amino- 6 pentyl)-4-amino-triazole in 50 ml. of water anddried for 24 hours in a tumbler drier at and 0.5 Torr under a protectivegas and thereupon spun into fibrous filaments.

Properties of the span polycondensates In Table 1, several condensatesprovided with additives according to the invention are compared with acontrol condensate which contains no additive.

TABLE 1.COMPARISON OF TEXTILE DATA Stretch Breaking Ex Additives Z 10Denier ratio Strength stretch,

percent 9 None 9.05 30/9 L3 12 33.2 24.9 7 9.72 30/9 1.3 12 33.2. 25.31U 9.91 30/9 1.3 12 31.8 27.1

In Table 2, the dyeability of modified polycondensates producedaccording to the invention is compared with the dyeability of thecontrol condensate according to Example 9. beach case, 3.5 g. of afabric of filaments having a denier of 30/9 were dyed in a 1% dyestuffsolution until the bath was exhausted. For the appraisal of thedyeability, the remission degrees were determined. (Measurement wascarried out with Elrepho apparatus, filter R 42.)

TABLE 2.COMPARISON OF DYEABILITY BY THE DEGREE OF REMISSION Example No.4 (1 Example N o. 7 (0.5 mol. percent additive mol. percent additiveDyestuil condensed-in) panned-011) Modified Control Modified ControlAnthralau blue B 19. 6 24. 1 20. 7 23. 5 Petllton blue B 26. 7 29. 8 27.3 29. 1 Cibalan blue B L 9. 5 11.9 9. 9 11. 4.

APPENDIX Example 11.Pr0duction ofbis-3,5-(4-aminocyclohexyl)-4-aminotriaz0le: 4.0 g. ofhexahydro-p-aminobenzoic acid-lactam are heated with 7.0 g. of freshlydistilled hydrazine hydrate in a bomb tube under a nitrogen atmospherefor 6 hours at 210 C. After distilling off the volatile components fromthe reaction product on a boiling Water bath under the reduced pressureof a water jet vacuum, there remains after cooling a colorless solidglassy mass. The powdered mass is extracted for several times with etherand once with cyclohexane for cleaning. The product is soluble in waterand represents the mixture of the cis-trans-isomers. The yield is 85% ofthe theoretical amount.

The invention is hereby claimed as follows:

1. A process for the production of abis-3,5-(w-aminoalkyl)-4-aminotriazole which comprises reacting a lactamwith hydrazine at a temperature between about C. and 250 C. and in thepresence of an inert gas.

2. A process as claimed in claim 1 wherein the reaction temperature isabout 180 C. to 230 C.

3. A process as claimed in claim 1 wherein said hydrazine is introducedinto the reaction as hydrazine hydrate.

7 4. A compound of the formula wherein R represents a member selectedfrom the group consisting of C H and n being an integer of from 3 to 7,inclusive.

5. A process as claimed in claim 1 wherein said reaction is carried outat a pressure of about 30 to 70 atmospheres.

6. A process as claimed in claim 1 wherein said lactam is reacted with amolar excess of said hydrazine.

7. Bis-3,S-(w-aminopropyl)-4-aminotriazole.

8. Bis-3,5-(w-aminopentyl)-4-aminotriazo1e.

9. Bis-3,5-(4-aminocyclohexyl)-4-aminotriazole.

References Cited by the Examiner UNITED STATES PATENTS FOREIGN PATENTSJapan.

OTHER REFERENCES Taniyama et a1., Kogyo Kagaku Zasshi, Vol. 64, pagesA99 and 1626-8 (1961).

NICHOLAS S. RIZZO, Primary Examiner. 20 J. R. LIBERMAN, Examiner.

1. A PROCESS FOR THE PRODUCTION OF ABIS-3,5-(W-AMINOALKYL)-4-AMINOTRIAZOLE WHICH COMPRISES REACTING A LACTAMWITH HYDROZINE AT A TEMPERATURE BETWEEN ABOUT 150*C. AND 250*C. AND INTHE PRESENCE OF AN INERT GAS.
 4. A COMPOUND OF THE FORMULA